Compounds

ABSTRACT

The present invention relates to compounds according to formula (Ia) or formula (Ib); 
                         
wherein each W is independently selected from the group consisting of H, F, Cl, Br, I and (CY 2 ) m CY 3 ; each Y is independently selected from the group consisting of F, Cl, Br and I; each Z is independently selected from the group consisting of H, OH, (CW 2 ) p CW 3 , CY 3 , OCW 3 , O(CW 2 ) p CW 3 , OCW((CY 2 ) m CY 3 )CWCW 2 , (CW 2 ) p OH, polyalkylene glycol and polyolester; n is an integer from 2 to 49; m is an integer from 0 to 3; p is an integer from 0 to 9; the molecular weight average (M W ) is ≤5500; and the polydispersity index is ≤1.45; compositions comprising these compounds and methods for their production.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is the U.S. national stage of international applicationPCT/GB2019/053650, filed Dec. 20, 2019, which claims priority fromGB1910153.4 filed on Jul. 16, 2019 and GB1820989.0 filed on Dec. 21,2018, the entireties of which are hereby fully incorporated by referenceherein.

The present invention relates to compounds, compositions, uses thereofand methods for preparing the same. The compounds of the invention arehalogenated polyethers. The compositions of the invention comprise aheat transfer portion and a lubricating portion, wherein the lubricatingportion comprises a halogenated polyether. The compositions of theinvention may be used in refrigerants and refrigerant blends. Thecompounds of the invention may be produced by polymerisation offluorinated epoxides.

The listing or discussion of a prior-published document in thisspecification should not be necessarily taken as an acknowledgement thatthe document is part of the state of the art or is common generalknowledge.

Fluorocarbon-based compounds are currently used in a large number ofcommercial and industrial applications, such as propellants, blowingagents and heat transfer fluids. The interest in, and use of,fluorine-based compounds, particularly (hydro)fluoroolefins, as heattransfer fluids has increased as new refrigerants are sought.

Dichlorodifluoromethane (refrigerant R-12) possesses a suitablecombination of refrigerant properties and was, for many years, the mostwidely used refrigerant. Due to international concern that fully andpartially halogenated chlorofluorocarbons, such asdichlorodifluoromethane and chlorodifluoromethane, were damaging theearth's protective ozone layer, there was general agreement that theirmanufacture and use should be severely restricted and eventually phasedout completely. The use of dichlorodifluoromethane was phased out in the1990s.

Chlorodifluoromethane (R-22) was introduced as a replacement for R-12because of its lower ozone depletion potential. Following concerns thatR-22 is a potent greenhouse gas, its use is also being phased out.R-410A and R-407 (including R-407A, R-407B and R-407C) have beenintroduced as a replacement refrigerant for R-22. However, R-22, R-410Aand the R-407 refrigerants all have a high global warming potential(GWP, also known as greenhouse warming potential).

1,1,1,2-tetrafluoroethane (refrigerant R-134a) was introduced as areplacement refrigerant for R-12. However, despite having a low ozonedepletion potential, R-134a has a GWP of 1430. It would be desirable tofind replacements for R-134a that have a lower GWP.

R-152a (1,1-difluoroethane) has been identified as an alternative toR-134a. It is somewhat more efficient than R-134a and has a greenhousewarming potential of 120. However, the flammability of R-152a is judgedtoo high, for example to permit its safe use in mobile air conditioningsystems. In particular its lower flammable limit in air is too low, itsflame speeds are too high, and its ignition energy is too low.

R-410A is a non-flammable mixture of R-32 (difluoromethane) and R-125(pentafluoroethane) in the proportions 50%/50% by weight. It isextensively used as an air-conditioning refrigerant but has a GWP of2107. It is desirable to find replacements for R-410A that have a lowerGWP.

R-32 has been proposed as a lower-GWP replacement for R-410A but it isflammable. In addition, R-32 can exhibit regions of liquid-liquidimmiscibility in combination with Polyolester (POE) refrigerationlubricants. R-32 can also exhibit higher solubility in POE lubricantsthan R-410A, reducing the effective viscosity of the lubricant phase.This can lead system designers to recommend higher viscosity gradelubricant for use with R-32 than with R-410A, which can reduce thecompressor efficiency. It would thus be desirable to find a combinationof R-32 with lubricant which reduced the flammability, improved mutualmiscibility and/or gave an acceptable solubility of refrigerant inlubricant and vice versa.

Carbon dioxide (R-744) is finding increasing use as a refrigerant forstationary and mobile air-conditioning and refrigeration applications.It is commonly used with Polyalkylene Glycol (PAG) lubricants.Conventional PAG lubricants exhibit extensive regions of liquidimmiscibility with R-744 which can lead to heat transfer problems in theevaporator of systems using this type of heat transfer composition. Itwould be advantageous to identify a lubricant which had improvedmiscibility with R-744 and whose combination with R-744 was an improvedheat transfer composition.

PAG lubricants also exhibit hygroscopicity, which in systems using R-744can lead to formation of carbonic acid and hence system corrosion. Itwould be advantageous to find a heat transfer composition comprisingR-744 with reduced hygroscopicity.

(Hydro)fluoroolefins, particularly tetrafluoropropenes, have beenproposed as possible refrigerants for use in a variety of heat transferdevices.

Heat transfer fluids are often used in combination with lubricants, suchas in heating and refrigeration systems. Such lubricants are included inheat transfer compositions to ensure continued smooth operation of theheat transfer system.

It is necessary that lubricants used in heat transfer compositions arecompatible with the refrigerants in the compositions. The compatibilityof the lubricant and the refrigerant is predicated on a number offactors, such as a desire for at least partial miscibility at part ofthe operating temperature range, a low tendency to degrade or react inuse and appropriate viscosities for the application.

However, in much of the prior art on the polymerisation and polymers oftrifluoropropylene oxide it is clear that the methods used, and theproducts produced by these methods would be unsuitable for use inlubricating and heat transfer compositions with refrigerants andrefrigerant blends that include (hydro)fluoroolefins.

The polymers produced by these methods often produce solid or veryviscous polymers with molecular weights that exceed 50000.

WO 2017/098238 describes compositions which comprise a heat transferportion and a lubricating portion, wherein the lubricating portioncomprises a halogenated polyether. The method to polymerise thefluorinated epoxides described in WO 2017/098238 may not be ideal forexploitation on an industrial scale.

There is, therefore, a need for lubricants that can be used inconjunction with heat transfer fluids for the use in refrigerantsystems. In order to match these requirements a lubricant which has aM_(W) of ≤5500 and a polydispersity index of ≤1.45 is desirable.

There is, therefore, a need for lubricants that can be used inconjunction with heat transfer fluids, both those currently used andthose proposed as replacement compositions. In particular, lubricantsare desired that are miscible with a wide range of heat transfer fluids,possess an appropriate viscosity, do not reduce the performance of heattransfer fluids and have low flammability; all in addition tosuccessfully functioning as a lubricant.

In addition, there is a need for a method which can produce saidpolymers without the need for a hazardous initiator and/or solvent,and/or reduce the reaction time from days to hours, and/or enable goodcontrol of the properties of the polymers produced.

Lubricants with low flammability are particularly important for heattransfer fluids that are used in air-conditioning applications such asmobile air-conditioning, as such compositions are in danger of cominginto contact with hot metal surfaces of the engine. Likewise, instationary residential air-conditioning applications, it is often thecase that the air-conditioning unit is located near to the building'sheating furnace and thus if a flammable refrigerant is used in thisapplication there is a risk of leaked heat transfer composition hittinghot furnace surfaces.

The subject invention addresses the above and other deficiencies by theprovision of a compound according to formula (Ia) or formula (Ib):

whereineach W is independently selected from the group consisting of H, F, Cl,Br, I and (CY₂)_(m)CY₃;each Y is independently selected from the group consisting of F, Cl, Brand I;each Z is independently selected from the group consisting of H, OH,(CW₂)_(p)CW₃, CY₃, OCW₃, O(CW₂)_(p)CW₃, (CW₂)_(p)OH, polyalkylene glycoland polyolester; n is an integer from 2 to 49;m is an integer from 0 to 3;p is an integer from 0 to 9;the molecular weight average (M_(W)) is ≤5500; andthe polydispersity index is ≤51.45.

For example, wherein

each W is independently selected from the group consisting of H, F, Cl,Br and I;

each Y is independently selected from the group consisting of F, Cl, Brand I;

each Z is independently selected from the group consisting of H, OH,(CW₂)_(p)CW₃, CY₃, OCW₃, O(CW₂)_(p)CW₃, polyalkylene glycol andpolyolester;

n is an integer from 2 to 49;

m is an integer from 0 to 3;

p is an integer from 0 to 9;

the molecular weight average (M_(W)) is ≤5500; and

the polydispersity index is ≤1.45.

For example, at least one (CY₂)_(m)CY₃ may be CF₃ (i.e.: m=0 and each Yis F).

For example, (CY₂)_(m)CY₃ may be CF₃ and at least one W may also be(CY₂)_(m)CY₃. In particular, each (CY₂)_(m)CY₃ group may be CF₃.

Examples of compounds of formula Ia and Ib include compounds in which(CY₂)_(m)CY₃ is CF₃, one W is CF₃ and each other W group is H. Furtherexamples include compounds in which (CY₂)_(m)CY₃ is CF₃, one or twogroups W are F and one or two W groups are H (e.g. two W groups are Hand one W group is F).

When each repeating unit in the compounds of the invention contains twogroups (CY₂)_(m)CY₃, such as two CF₃ groups, these may be connected tothe same carbon atom or adjacent carbon atoms in the chain or backbone.

The compound of formula (Ib) may alternatively be represented by thefollowing formula (Ic):

The compound of formula (Ia), (Ib) and (Ic) may have a M_(W) of ≤4000,preferably ≤3000, even more preferably ≤2500.

The compound of formula (Ia), (Ib) and (Ic) may have a polydispersityindex of about 1.45, preferably about 1.35, more preferably about 1.30,even more preferably about 1.25.

Y is preferably F or Cl, more preferably Y is F.

W is preferably H, F or Cl. More preferably W is H.

Advantageously, m is an integer from 0 to 3, preferably 0.

n is preferably an integer from 2 to 49, for example 5 to 25, preferablyn is an integer from 6 to 20, e.g. 6, 7, 8, 9, 10, 11, 12, 13, 14, 15,16, 17, 18, 19, 20.

It will be understood that references to formula (I) refer to formula(Ia), formula (Ib) and/or formula (Ic).

In some compounds of formula (I), at least one, and in some cases both,of the Z derivatives are not H or OH.

In some compounds of formula (I), at least one Z derivative may comprisea polyalkylene glycol. Alternatively, both Z derivatives may comprise apolyalkylene glycol (PAG). In both instances, the polyalkylene glycolmay be selected from the group consisting of poly(ethylene) oxide,poly(propylene) oxide, and mixtures thereof. In such embodiments, thePAG groups may be conjugated to the compound of formula (I) through theformation of an ester bond between a hydroxyl end-capping group offormula (I) (i.e., Z═OH or Z═(CW₂)_(p)OH) with a carboxylic acidend-capped PAG.

In some compounds of formula (I), at least one Z derivative may comprisea fluorinated-PAG (F-PAG). The F-PAG may be selected from the groupconsisting of F₃C— end capped PAGs and hydroxyl end capped PAGs.

The hydroxyl end groups of F-PAGs can provide further scope forderivatisation and can, for example, be converted to ether or estergroups. These groups can be aliphatic, aromatic, linear, branched,fluorine containing or functionalised in other ways to allow for furtheradjustments to the properties of the products.

The inventors have found that when at least one Z derivative comprises aF-PAG, the lubricating properties of the compound of formula (I) may beimproved.

In some compounds of formula (I), the Z derivative may, independently,be an alkyl or alkoxy group containing from 1 to 10 carbon atoms.

Both Z derivatives may be the same. Alternatively, both Z derivativesmay be different.

p is preferably an integer from 1 to 6, more preferably 2 to 6, forexample 3 to 5.

The compound of formula (I) may for example have a viscosity at 40° C.of from about 5 to about 250 cP. The compound of formula (I) may have aviscosity at 40° C. of from about 15 to about 150 cP.

The compound of formula (Ia) may be a compound of formula (IIa):

The compound of formula (Ib) may be a compound of formula (IIb):

Alternatively, or additionally, the compound of formula (Ia) may be acompound of formula (IIIa):

Alternatively, or additionally, the compound of formula (Ib) may be acompound of formula (IIIb):

The skilled person will understand that the above formulas arerepresentative only and that it will be appreciated that structuraldefects may exist in the polymer chains.

A composition may, for example, comprise at least two differentcompounds of formula (I). In such instances, the value of n may be thesame for the at least two compounds of formula (I). Alternatively, thevalue of n may be different for the at least two compounds of formula(I).

Preferably, the compound of formula (I) is a compound of formula (Ib).

The compound of formula (I) may be a mixture of compounds of formula(Ia) and (Ib). In this situation, it is preferable that the majority ofthe mixture is a compound of formula (Ib), for example greater than 50%by weight of the mixture is a compound of formula (Ib), preferablygreater than 75%, more preferably greater than 90% or 95%.

The compound of formula (I) may be made by a method comprising thepolymerisation of an epoxide precursor.

The epoxide precursor preferably has the formula (IV)

wherein:R₁ is (CY₂)_(m)CY₃;R₂ is H, F, Cl, Br, I or (CY₂)_(m)CY₃;R₃ is H, F, Cl, Br, I or (CY₂)_(m)CY₃;R₄ is H, F, Cl, Br, I or (CY₂)_(m)CY₃.

For example, wherein

R₁ is CF₃;

R₂ is H, F or CF₃;

R₃ is H, F or CF₃;

R₄ is H or CF₃.

For example, wherein

R₁ is CF₃;

R₂ is H or F;

R₃ is H or F;

R₄ is H or CF₃.

Examples of the epoxide precursors that may be used include an epoxideaccording to formula (IV), wherein R, is CF₃, R₂ is H, R₃ is H, R₄ is H(the epoxide of 3,3,3-trifluoropropene (1243zf)); an epoxide accordingto formula (IV), wherein, R, is CF₃, R₂ is F, R₃ is H and R₄ is H (theepoxide of 2,3,3,3-tetrafluropropene (1234yf)); an epoxide according toformula (IV), wherein R, is CF₃, R₂ is H, R₃ is F, R₄ is H (the epoxideof 1,3,3,3-tetrafluoropropene (1234ze)); an epoxide according to formula(IV), wherein R, is CF₃, R₂ is H, R₃ is CF₃, R₄ is H; an epoxide whereinR, is CF₃, R₂ is H, R₃ is H, R₄ is CF₃ (the epoxide of1,1,1,4,4,4-hexafluoro-2-butene (1336mzz)); and an epoxide wherein R, isCF₃, R₂ is CF₃, R₃ is H, R₄ is H (the epoxide3,3,3-trifluoro-2-(trifluoromethyl)-1,2-propenoxide (HFIBO)). Preferablythe epoxide is the epoxide of 1243zf (1,1,1-trifluoro-2,3-epoxypropane).

The method may comprise the polymerisation of an epoxide using aninitiator formed from a base and an alcohol.

Preferably, the base is a group I or group II metal hydroxide, morepreferably a group I metal hydroxide, even more preferably sodium orpotassium hydroxide, even more preferably potassium hydroxide.

Preferably, the alcohol is a primary alcohol. The primary alcohol may,for example, be a C₁ to C₁₀ glycol, preferably ethylene glycol. Theprimary alcohol may, for example, be a C₁ to C₁₀ branched or straightchain alcohol. The primary alcohol, for example, may be a fluorinatedalcohol, for example a C₁ to C₁₀ fluorinated alcohol, preferablytrifluoroethanol.

The polymerisation of the epoxide may be carried out in the absence ofsolvent.

The polymerisation reaction may be carried out at a temperature of fromabout 0 to about 130° C., preferably from about 40 to about 100° C.,more preferably from about 50 to about 90° C.

The polymerisation reaction may be carried out at a pressure of fromabout 100 to about 1000.3 kPa, preferably about 101 kPa.

The compound of formula (I) can be used as a lubricant.

The compound of formula (I) may form part of a composition, wherein thecompound of formula (I) is the lubricating portion and wherein thecomposition also comprises a heat transfer portion. Preferably, thecomposition comprises a single liquid phase across the entiretemperature range between −30° C. and 70° C.

The weight percentage of the lubricating portion in the totalcomposition of the invention may, for example, be from about 1 to about30%, preferably from about 1 to about 10%, more preferably from about 1to about 5%.

The heat transfer portion may comprise one or more compounds selectedfrom the group consisting of (hydro)fluoroolefins (HFOs),hydrofluorocarbons (HFCs), chlorofluorocarbons (CFCs),hydrochlorofluorocarbons (HCFCs), perfluoroalkyl iodides andhydrocarbons.

The heat transfer portion may, for example, comprise one or morecompounds selected from the group of 1,1,2,3,3,3-pentafluoropropene(R-1225ye), 1,3,3,3-tetrafluoropropene (R-1234ze),2,3,3,3-tetrafluoropropene (R-1234yf), 3,3,3-trifluoropropene(R-1243zf), 1,1,1,2-tetrafluoroethane (R-134a), 1,1-difluoroethane(R-152a), difluoromethane (R-32), fluoroethane (R-161),pentafluoroethane (R-125), 1,1,2,2-tetrafluoroethane (R-134), propane,propylene, carbon dioxide, 1,1,1,3,3-pentafluoropropane (R-245fa),1,1,1,3,3,3-hexofluoropropane (R-236fa), 1,1,1,2,2-pentafluoropropane(R-245cb), 1,1,1,2,3,3,3-heptafluoropropane (R-227ea),1,1,1-trifluoroethane (R-143a), n-butane, iso-butane and1,1,1,3,3-pentafluorobutane (R-365mfc), 1,1,2-trifluoroethylene(R-1123), 1,1-difluoroethylene (R-1132a), trifluoromethyl iodide (CF₃I),carbon dioxide (R-744), ethane (R-170), ethylene (R-1150), propene(R-1270), propane (R-290), isobutane (R-600a), n-butane (R-600),n-pentane (R-601) and isopentane (R-601a).

For the avoidance of doubt, it is to be understood that where a compoundmay exist as one of two configurational isomers, e.g. cis and transisomers around a double bond, the use of the term without isomerdesignation (e.g. R-1234ze) is to refer to either isomer.

The heat transfer portion may comprise tetrafluoropropenes. Preferably,the heat transfer portion comprises R-1234ze, even more preferably theheat transfer portion comprises R-1234ze(E).

The heat transfer composition may comprise R-1234yf.

The heat transfer composition may comprise CF₃I.

The heat transfer composition may comprise R-32.

The heat transfer composition may comprise R-32 and R-1234yf.

The heat transfer composition may comprise R-1132a, R-1123 orcombinations of one or more of these with R-32.

The heat transfer composition may comprise a hydrocarbon selected fromR-170, R-1150, R-1270. R-290, R-600a, R-600, R-601 and R-601a.

The heat transfer composition may comprise R-744.

Some compositions of the invention are less flammable than a compositioncomprising the same heat transfer portion combined with a polyalkyleneglycol (PAG) and/or a polyol ester (POE) based lubricant.

The composition of the invention may be miscible with existingpolyalkylene glycol, polyalkylene glycol ester and polyol esterlubricating oils.

The compounds comprising the lubricating portion typically comprisecarbon, hydrogen and oxygen, with a ratio of oxygen to carbon sufficientto provide a degree of miscibility with the heat transfer portion, suchas when the lubricating portion is added to the heat transfer portion ina proportion of from about 1 to 30 wt %, preferably 1 to 10 wt % andeven more preferably 1 to 5 wt % of the total composition, the mixturehas one liquid phase. Preferably, the mixture has one liquid phase when1 to 20 wt % of the lubricating portion is present in the composition.Even more preferably, the composition is one liquid phase regardless ofthe proportions of the heat transfer portion to the lubricating portion.This solubility or miscibility preferably exists at all normal operatingtemperatures. For example, the solubility or miscibility exists at leastone temperature between −100° C. and +100° C., preferably at least onetemperature between −75° C. and +75° C. and even more preferably, atleast one temperature between −50° C. and +50° C. Advantageously, thesolubility or miscibility exists over all temperature ranges wherein thecomposition is in the liquid phase.

Conveniently, the compositions of the invention (comprising a compoundof formula (I) and a heat transfer compound or heat transfer portion)are less flammable than the heat transfer compound or heat transferportion alone.

Preferably, the composition of the invention has a lowest temperature ofignition of about 500° C. or greater, such as about 510° C., 520° C.,530° C., 540° C., 550° C., 560° C., 570° C., 580° C., or 590° C.,preferably about 600° C. or greater, for example about 610° C., 620° C.,630° C. or 640° C.

Advantageously the compositions of the invention have reducedhygroscopicity compared to heat transfer compositions comprisingnon-halogenated PAG or polyether lubricants.

The composition of the invention may be non-flammable.

Flammability may be determined in accordance with ASHRAE Standard 34incorporating the ASTM Standard E-681 with test methodology as perAddendum 34p dated 2004, the entire content of which is incorporatedherein by reference.

Conveniently, the Global Warming Potential (GWP) of the compositions ofthe invention may be less than about 3500, 3000, 2500 or 2000. Forinstance, the GWP may be less than about 2500, 2400, 2300, 2200, 2100,2000, 1900, 1800, 1700, 1600 or 1500. The GWP of the compositions of theinvention preferably is less than 1400, 1300, 1200, 1100, 1000, 900,800, 700, 600 or 500.

Preferably, the compositions of the invention have zero or near zeroozone depletion.

The compositions of the invention may have improved heat transferproperties than the heat transfer fluid alone.

Without wishing to be bound by theory, it is believed that compounds offormula (I) may further act as heat transfer agents and thereforeincrease the heat transfer properties of the compositions of theinvention.

The composition may optionally comprise a stabiliser, preferably thestabiliser is selected from diene-based compounds, phosphates, phenolcompounds and epoxides, and mixtures thereof.

The composition may optionally comprise a flame retardant. Preferably,the flame retardant is selected from the group consisting oftri-(2-chloroethyl)-phosphate, (chloropropyl) phosphate,tri-(2,3-dibromopropyl)-phosphate, tri-(1,3-dichloropropyl)-phosphate,diammonium phosphate, various halogenated aromatic compounds, antimonyoxide, aluminium trihydrate, polyvinyl chloride, a fluorinatediodocarbon, a fluorinated bromocarbon, trifluoro iodomethane,perfluoroalkyl amines, bromo-fluoroalkyl amines and mixtures thereof.

The composition may also comprise an anti-wear additive, such astricresyl phosphate.

The composition of the invention may be comprised within a lubricantcomposition in a proportion of at least about 10 to about 90 wt %,preferably in a proportion of about 10 to about 75 wt %, such as about10, 20, 30, 40 or 50 wt %.

The invention also provides a heat transfer device containing acomposition of the invention and/or the use of a composition of theinvention in a heat transfer device.

The heat transfer device may, for example be a refrigeration device.

The heat transfer device may, for example, be selected from the groupconsisting of automotive air conditioning systems, residential airconditioning systems, commercial air conditioning systems, residentialrefrigerator systems, residential freezer systems, commercialrefrigerator systems, commercial freezer systems, chiller airconditioning systems, chiller refrigeration systems, and commercial orresidential heat pump systems.

Preferably, the heat transfer device contains a compressor.

In an aspect of the invention, there is provided a method of cooling anarticle, which comprises condensing a composition of the invention andthereafter evaporating the composition in the vicinity of the article tobe cooled.

In a further aspect of the invention, there is provided a method forheating an article, which comprises condensing a composition of theinvention in the vicinity of the article to be heated and thereafterevaporating the composition.

In a further aspect of the invention, there is provided a mechanicalpower generation device containing a composition of the invention.

Preferably, the mechanical power generating device is adapted to use aRankine Cycle or modification thereof to generate work from heat.

There is also provided a method of retrofitting a heat transfer devicecomprising the step of removing an existing heat transfer fluid andintroducing a composition of the invention. Preferably, the heattransfer device is a refrigeration device. Preferably, the heat transferdevice is an air-conditioning system.

There is also provided a method of reducing the flammability of acomposition by the addition of a composition of the invention.

Compositions of the invention comprising a heat transfer portion may,for example, be prepared by mixing one or more compounds of formula (I)with a heat transfer fluid.

In an aspect of the invention, the composition may be used as a heattransfer agent. When used as a heat transfer agent, the compositions ofthe invention may optionally comprise at least two compounds accordingto formula (I).

In another aspect, the compositions of the invention may be used aslubricants. In a further aspect, the lubricant composition may compriseat least two compounds according to formula (I).

The use of effective amounts of compounds according to formula (I) in alubricant composition or a heat transfer composition is advantages dueto their thermal and mechanical stability, lubricity, viscosity, pourpoint, anti-oxidation and anti-corrosive properties.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a graph showing the viscosity-temperature profile for thereference oil, Supercool PAG 46 (a commercial PAG refrigerationlubricant) and Example 5-F(F).

FIG. 2 is the Gel Permeation Chromatography (GPC) analysis of SupercoolPAG 46.

FIG. 3 is the GPC analysis of Example 5-F(F).

FIG. 4 is the Vapour-Liquid Equilibria data for R-1234yf and Example5-F(F).

FIG. 5 is the Vapour-Liquid Equilibria data for R-1234yf and SupercoolPAG 46 reference oil.

EXAMPLES

The invention is illustrated by the following non-limiting examples.

Compounds according to the invention were synthesised by the followingmethod.

General Method:

An initiator mixture was prepared by adding, with stirring and cooling,a quantity of base (e.g. 85-86% KOH) to an alcohol (e.g. ethylene glycolor trifluoroethanol) in a Pyrex round 25 bottomed flask along with 2-3drops of Aliquat 336. When the base had dissolved in the alcohol thereaction flask was equipped with a dropping funnel and a condenserbefore the epoxide monomer (e.g. 3,3,3-trifluoro-1,2-epoxypropane) wasadded. The mixture was then heated with stirring for a fixed period. Atthe end of the reaction the product was cooled and dissolved in aminimum quantity of chloroform (e.g. 250 ml). This chloroform solutionwas washed with acidified water (e.g. 4 g 36% HCl in 100 ml water) andthen three times with water alone (e.g. 100 ml). The washed chloroformsolution of the polymer product was dried over anhydrous sodium sulphateand after filtration the solvent was removed by distillation at reducedpressure.

The polymer products obtained were analysed and characterised by:

Gel permeation chromatography (GPC): GPC was performed on a ShimadzuProminence LC system equipped with an RI detector with a 300 mm×75 mm, 5μm PLgel 100 Å and 300 mm×7.5 mm, 5 μm PLgel 500 Å column in series at40° C. with a THF eluent at 1.0 ml/min. The method was calibrated withpoly(styrene) standards with MW between 1000 and 10000.

Viscometry: Viscometry was performed on a TA Instruments DiscoveryHybrid Rheometer using a 40 mm 2.008° cone plate geometry at 10 rad/sbetween −20 and 70° C.

Using this general method, a series of polymer products were produced.Details for each preparation and key properties of each product areoutlined in the Table 1. Table 1 also contains data from a referenceexample: the commercial refrigeration lubricant Supercool PAG 46.

TABLE 1 Preparative examples Recipe Batch GPC Analysis Initiator TFPOTemperature Yield time M_(w)/M_(n) Viscometry, η (cP) at ° C. Example(g) (g) (° C.) (g) (hrs) M_(n) M_(w) (PDI) −10 0 20 40 60 1 - F(A) EG5.7 130.8 70 121.2 72 1078 1307 1.21 27122.2 7154.3 599.1 125.5 46.8 KOH1.07 2 - F(B) EG 5.34 135.8 50 118.6 72 1139 1379 1.22 28106.1 7341.6627.7 132.4 49.3 KOH 1.0 3 - F(C) EG 5.1 135.0 90 129.1 72 2069 23991.16 25726.3 6904.9 613.0 134.3 49.5 KOH 1.1 4 - F(D) TFEA 1.1 135.8 70127.9 48 1516 1712 1.13 16917.8 4267.3 444.0 109.4 44.5 KOH 1.1 5 - F(F)TFEA 10 135 70 86.3 48 1478 1401 1.05 3066.9 824.9 130.2 40.1 18.1 KOH2.0 Reference N/A N/A N/A N/A N/A 1141 1886 1.65 568.5 271.3 84.0 37.021.4 example: Supercool PAG 46 *EG = Ethylene glycol, TFEA =trifluoroethanol, TFPO = 3,3,3 -trifluoro-2,3-epoxypropane

The results clearly show that by using the method of the inventionpolymers could be simply and easily produced with a significantimprovement of molecular weight control (M_(W) and M_(n)) andpolydispersity index (PDI) when compared to the reference example(Supercool PAG 46, a commercial PAG refrigeration lubricant). Theproperties of the product of example 5-F(F) were particularly good andthe viscometry and GPC results for the Reference Example and Example5-F(F) are shown in FIGS. 1-3 .

Vapour-Liquid Equilibria (VLE)

Vapour-liquid equilibria data was measured in a static constant-volumeapparatus consisting of a vessel of a precisely known internal volume,located in a temperature-controlled metal block. A magnetic stirringdevice was located inside the heated vessel. Heat transfer fluid,controlled at a constant temperature, was passed through the block toallow precise control of temperature inside the vessel. The cell wasevacuated and then known amounts of each component were charged to thecell. The temperature of the cell was then varied stepwise from about−30° C. to +70° C. At each temperature, the cell temperature andpressure were logged continuously and recorded when stable conditionswere reached.

The vapour-liquid equilibria data was measured for R-1234yf and theproduct of Example 5-F(F), as shown in FIG. 4 . The system displayspositive deviation from ideal behaviour and the raw experimental datashows that there is no region of liquid-liquid immiscibility over thetemperature and composition range studied.

The vapour-liquid equilibria data was measured for R-1234yf andSupercool PAG 46, as shown in FIG. 5 . The data shows that a region ofliquid-liquid immiscibility may be present for mixtures at compositions60% w/w R-1234yf and above. Below 50% w/w R-1234yf mixtures, noimmiscibility is expected over the temperature range studied.

The results show that the product of Example 5-F(F) and R-1234yf aremiscible in all proportions. The same miscibility cannot be seen withthe commercial PAG refrigeration lubricant (Supercool PAG 46) andR-1234yf. Therefore, the product of Example 5-F(F) shows betterproperties than the commercial lubricant.

Example 6

Polymerisations Involving3,3,3-trifluoro-2-(trifluoromethyl)-1,2-propenoxide (HFIBO)

An initiator mixture was prepared by dissolving potassium hydroxide(85%, 0.27 g) in trifluoroethanol (1.25 g) with two drops of Aliquat 336in a round bottomed flask. The mixture was stirred under cooling untilall the KOH pellets had dissolved. Upon dissolution the flask wastransferred to a hotplate, equipped with a condenser and3,3,3-trifluoro-2-(trifluoromethyl)-1,2-propenoxide (16.25 g) added viaa dropping funnel. The hotplate was then heated to 70° C. and themixture began refluxing at 40° C. After refluxing for 24 hours a viscouspolymer had formed, and the temperature of the reaction mixture was 60°C. After cooling and washing the polymer was found to dissolve intetrahydrofuran and was analysed by ¹⁹F NMR spectroscopy which showedseveral very broad signals characteristic of polymers at −74.28, −75.08,−76.69 and −78.79 ppm (vs perfluorbenzene at −164.9 ppm). Evaporation ofthe solvent yielded a viscous white polymer.

Example 7

Polymerisations Involving 75% TFPO and 25% HFIBO

An initiator mixture was prepared by dissolving potassium hydroxide(85%, 0.26 g) in trifluoroethanol (1.25 g) with two drops of Aliquat 336in a round bottomed flask. The mixture was stirred under cooling untilall the KOH pellets had dissolved. Upon dissolution the flask wastransferred to a hotplate and3,3,3-trifluoro-2-(trifluoromethyl)-1,2-propenoxide (5.63 g) and TFPO(10.5 g) was added via a dropping funnel. The hotplate was then heatedto 70° C. and the mixture began refluxing at 40° C. the flask wasequipped with a chiller supplied condenser. After refluxing for 24 hoursa polymer had formed, and the temperature of the reaction mixture was65° C. After cooling the polymer was washed dissolution was attempted inchloroform, this layer was then washed and dissolved in tetrahydrofuranand analysed by ¹⁹F NMR spectroscopy which showed several very broadsignals characteristic of polymers at −73.61, −74.14, −75.89, −77.17 and−79.32 ppm (vs perfluorbenzene at −164.9 ppm). Evaporation of thesolvent yielded a grey coloured polymer.

Comparative Examples

Comparative examples were carried out using a commercial PAGrefrigeration lubricant (Supercool PAG 46) and the methods and productof Example 1 of WO 2017/098238.

The results clearly show a significant improvement in molecular weightcontrol and polydispersity index when an initiator of ethylene glycol ortrifluoroethanol and potassium hydroxide is used in the absence ofsolvent, see Table 2.

TABLE 2 Comparative examples GPC Analysis Recipe M_(w)/M_(n) Viscometry,η (cP) at ° C. Experiment Initiator (g) TFPO Temperature M_(n) M_(w)(PDI) −10 0 20 40 60 Reference N/A N/A N/A 1141 1886 1.65 568.5 271.384.0 37.0 21.4 example: Supercool PAG 46* Comparative t-BuOK 1.3 50 904063 5964 1.47 90100.4 21873.1 2153.7 435.7 158.4 Example 1: Example 1WO2017/098238 Comparative EG 2.53 43.6 90 3722 4303 1.16 42921.1 14167.81274.1 269.97 102.9 Example 2: t-BuOK 5 Solvent free Comparative TFEA 149.4 110 1469 1815 1.24 10046.3 2460.2 248.6 60.3 24.4 Example 3: t-BuOKSolvent free, 1.16 change alcohol Comparative EG 1.0 50 89 947 1118 1.189354.2 2403.4 261.6 60.6 23.0 Example 4: KOH 1.11 Solvent free, changebase *t-BuOK = potassium t-butoxide, EG = Ethylene glycol, TFEA =trifluoroethanol, TFPO = 3,3,3-thfluoro-2,3-epoxypropaneDevelopments of the Method of Preparation and Product of Example 5-F(F)

The procedure described above was used to prepare a series of variantsof the product of example 5-F(F) by varying the composition of theinitiator mix. Details for each individual preparation and results arepresented in Table 3.

In these examples the number of repeating units in the polymer products,n, was estimated by GPC which showed that polymers could be made with nin the range of 6-34 or so.

Lubricating Properties of Polymers

The lubricating properties of the polymer products from the method andproduct development examples were determined using a TA InstrumentsDiscovery Hybrid Rheometer by measuring the co-efficient of frictionbetween a rotating ball bearing and three fixed ball bearings at 25° C.at different sliding speeds as a function of axial force, see Table 4.

The results confirm that the polymers of the invention are excellentlubricants on a par with Supercool PAG 46, which is a fully formulatedcommercial lubricant whose formulation includes additives designed toaid lubricity.

TABLE 3 Development of the method of preparation and product of Example5 - F(F) n at n at n at n at n at TFEA KOH TFPO Polymer n −10° C. −0° C.20° C. 40° C. 60° C. Example (g) (g) (g) yield (g) M_(w) M_(n) PDI (GPC(cP) (cP) (cP) (cP) (cP) 5 - F(F) 10 2 135 86.3 1478 1401 1.05 11 3066.9824.9 130.2 40.1 18.1 5 - F(F) 22.3 4.54 300 280 1706 1615 1.06 136548.0 1532.5 231.7 62.3 25.7 Scale up** 1a 5 1 65 39 1217 1154 1.05 9829.2 263.5 53.0 18.4 8.8 2a 5 0.29 65 49.63 1403 1335 1.05 11 2491.9683.5 113.0 35.2 15.7 3a 5 1 65.4 52.6 1463 1385 1.06 11 2731.7 740.3119.6 36.8 16.3 4a 8.45 1 65 51.6 1036 995 1.04 7 335.8 121.9 29.2 11.05.4 5a 1.46 1 65 26.4 4032 3504 1.15 34 45437.0 12200.9 1113.8 235.287.1 6a 7.5 1.5 65 65 1280 1217 1.05 10 1391.4 414.3 76.1 25.1 11.8 7a7.5 0.5 64.93 25.2 842 825 1.02 6 73.6 33.3 10.1 4.3 2.1 7b 7.5 0.564.93 25.2 929 902 1.03 6 187.9 75.9 20.5 8.3 4.2 8a 5 1 65.3 53.1 14861408 1.06 11 2749.2 740.0 113.8 34.7 15.2 9a 2.5 1.5 65.1 55.5 2756 25781.07 23 22562.1 5398.8 528.5 121.9 46.2 10a 5 1.71 64.9 57.71 1648 15541.06 13 4256.9 1050.4 149.2 43.1 18.9 11a 5 1 65 52.5 1419 1340 1.06 112390.8 629.0 102.1 31.8 14.1 12a 5 1 65 57.1 1530 1444 1.06 12 2939.4786.9 129.9 38.0 16.4 13a 2.5 0.5 65 39.73 2024 1910 1.06 16 10415.62408.8 311.3 81.8 33.0 *TFEA = trifluoroethanol, TFPO =3,3,3-trifluoro-2,3-epoxypropane **Because of the larger scale of thisexample the method was adapted. Thus, the initiator mix was prepared andheated to 70°C and then the TFPO was added over 3-4 hours

TABLE 4 Lubricity of polymers from method and product development studyAxial Coefficient of friction (μ) force at sliding speed (μm/sec):Polymer example (N) 20000 40000 60000 80000 Reference example: 5 0.0970.096 0.095 0.094 Supercool PAG 46 10 0.103 0.100 0.098 0.096 15 0.1050.101 0.098 0.096 20 0.107 0.102 0.100 0.098 25 0.108 0.104 0.102 0.10030 0.110 0.107 0.104 0.103 35 0.112 0.109 0.107 0.105 40 0.113 0.1110.109 0.107  5-F(F) 5 0.104 0.104 0.104 0.103 10 0.114 0.104 0.106 0.10615 0.118 0.099 0.104 0.106 20 0.120 0.104 0.106 0.106 25 0.121 0.1210.115 0.116 30 0.121 0.121 0.120 0.119 35 0.120 0.120 0.119 0.118 400.120 0.120 0.119 0.117  5 - F(F) Scale up 5 0.101 0.099 0.097 0.097 100.107 0.105 0.103 0.103 15 0.111 0.110 0.109 0.109 20 0.114 0.113 0.1130.112 25 0.116 0.116 0.116 0.114 30 0.118 0.118 0.118 0.117 35 0.1190.120 0.120 0.118 40 0.121 0.121 0.120 0.119  1a 5 0.102 0.101 0.1010.100 10 0.109 0.108 0.107 0.106 15 0.110 0.108 0.106 0.105 20 0.1090.107 0.106 0.105 25 0.109 0.108 0.107 0.106 30 0.111 0.109 0.108 0.10835 0.112 0.111 0.110 0.108 40 0.112 0.111 0.109 0.108  2a 5 0.104 0.1030.102 0.101 10 0.109 0.108 0.106 0.105 15 0.110 0.108 0.107 0.106 200.111 0.109 0.108 0.107 25 0.112 0.111 0.110 0.109 30 0.113 0.112 0.1110.111 35 0.114 0.114 0.113 0.112 40 0.115 0.115 0.115 0.114  3a 5 0.1060.106 0.105 0.105 10 0.113 0.111 0.110 0.109 15 0.115 0.114 0.112 0.11120 0.117 0.116 0.115 0.114 25 0.119 0.118 0.117 0.116 30 0.120 0.1190.118 0.117 35 0.121 0.120 0.119 0.118 40 0.121 0.120 0.120 0.119  4a 50.093 0.091 0.089 0.088 10 0.102 0.098 0.096 0.094 15 0.105 0.101 0.0990.098 20 0.108 0.105 0.103 0.102 25 0.111 0.108 0.106 0.105 30 0.1130.109 0.107 0.106 35 0.114 0.110 0.108 0.107 40 0.115 0.111 0.110 0.108 5a 5 0.102 0.098 0.096 0.096 10 0.111 0.114 0.118 0.118 15 0.121 0.1240.127 0.125 20 0.129 0.130 0.130 0.129 25 0.132 0.134 0.133 0.132 300.134 0.136 0.135 0.134 35 0.136 0.138 0.137 0.136 40 0.137 0.139 0.1380.136  6a 5 0.097 0.096 0.095 0.095 10 0.107 0.105 0.103 0.102 15 0.1100.109 0.108 0.106 20 0.113 0.112 0.111 0.110 25 0.115 0.114 0.113 0.11330 0.116 0.116 0.115 0.114 35 0.118 0.117 0.117 0.116 40 0.119 0.1190.118 0.117  7a 5 0.109 0.104 0.102 0.100 10 0.116 0.110 0.107 0.105 150.118 0.113 0.110 0.107 20 0.124 0.117 0.114 0.111 25 0.129 0.122 0.1170.115 30 0.132 0.125 0.120 0.116 35 0.132 0.124 0.120 0.117 40 0.1330.124 0.120 0.118  7b (7a repeat) 5 0.094 0.092 0.091 0.091 10 0.1010.085 0.086 0.085 15 0.104 0.102 0.101 0.100 20 0.107 0.104 0.103 0.10225 0.109 0.107 0.105 0.104 30 0.111 0.109 0.107 0.107 35 0.113 0.1100.109 0.108 40 0.114 0.110 0.109 0.108  8a 5 0.113 0.113 0.113 0.113 100.114 0.114 0.114 0.114 15 0.115 0.115 0.115 0.115 20 0.116 0.116 0.1150.115 25 0.119 0.118 0.117 0.115 30 0.118 0.117 0.116 0.115 35 0.1180.117 0.116 0.116 40 0.118 0.118 0.117 0.116  9a 5 0.113 0.115 0.1160.116 10 0.123 0.125 0.125 0.126 15 0.127 0.129 0.129 0.129 20 0.1300.131 0.131 0.130 25 0.133 0.134 0.133 0.131 30 0.134 0.136 0.135 0.13335 0.136 0.137 0.136 0.134 40 0.137 0.138 0.137 0.135 10a 5 0.103 0.1040.104 0.103 10 0.110 0.111 0.111 0.111 15 0.113 0.113 0.113 0.112 200.115 0.115 0.114 0.113 25 0.114 0.112 0.112 0.113 30 0.117 0.118 0.1170.116 35 0.119 0.119 0.118 0.117 40 0.119 0.119 0.118 0.118 11a 5 0.1130.112 0.112 0.112 10 0.114 0.114 0.113 0.113 15 0.115 0.114 0.114 0.11320 0.115 0.115 0.114 0.113 25 0.116 0.116 0.115 0.114 30 0.117 0.1170.116 0.115 35 0.118 0.117 0.117 0.116 40 0.118 0.118 0.117 0.116 12a 50.101 0.102 0.102 0.102 10 0.109 0.109 0.109 0.108 15 0.112 0.112 0.1110.110 20 0.115 0.114 0.113 0.113 25 0.116 0.116 0.115 0.114 30 0.1170.117 0.116 0.115 35 0.118 0.117 0.117 0.116 40 0.118 0.118 0.117 0.11613a 5 0.117 0.119 0.120 0.120 10 0.120 0.121 0.121 0.121 15 0.122 0.1220.122 0.121 20 0.124 0.123 0.123 0.123 25 0.125 0.125 0.125 0.124 300.125 0.126 0.126 0.125 35 0.126 0.126 0.126 0.126 40 0.126 0.127 0.1270.126

The invention claimed is:
 1. A compound according to formula (Ia) orformula (Ib);

wherein each W is independently selected from the group consisting of H,F, Cl, Br, I, and (CY₂)_(m)CY₃, provided that at least one W in thecompound according to formula (Ia) is (CY₂)_(m)CY₃; each Y isindependently selected from the group consisting of F, Cl, Br, and I;each Z is independently selected from the group consisting of H, OH,(CW₂)_(p)CW₃, CY₃, OCW₃, O(CW₂)_(p)CW₃, OCW((CY₂)_(m)CY₃)CWCW₂,(CW₂)_(p)OH, polyalkylene glycol (“PAG”), and polyester; n is an integerfrom 2 to 49; m is an integer from 0 to 3; p is an integer from 0 to 9;the molecule weight average (Mw) is ≤5500; and the polydispersity indexis ≤1.45.
 2. The compound according to claim 1 wherein each W in thecompound according to formula (Ib) is independently selected from thegroup consisting of H, F, Cl, Br, and I; and each Z is independentlyselected from the group consisting of H, OH, (CW₂)_(p)CW₃, CY₃, OCW₃,O(CW₂)_(p)CW₃, OCW((CY₂)_(m)CY₃)CWCW₂, polyalkylene glycol (PAG), andpolyolester.
 3. The compound according to claim 1 wherein the Mw is≤4000.
 4. The compound according to claim 1 wherein the polydispersityindex is about 1.40.
 5. The compound according to claim 1, wherein Y isF or Cl; and/or wherein W is H, F, Cl, or (CY₂)_(m)CY₃.
 6. The compoundaccording to claim 1, wherein one W group is (CY₂)_(m)CY₃, two W groupsare H, Y is F, and m is
 0. 7. The compound according to claim 1, whereinone or two W groups are F, one or two W groups are H, Y is F, and m is0.
 8. The compound according to claim 7, wherein one W group is F, andtwo W groups are H.
 9. The compound according to claim 1, wherein Zcomprises a polyalkylene glycol (PAG).
 10. The compound according toclaim 1, wherein at least one Z is not H or OH.
 11. The compoundaccording to claim 1, wherein at least one Z comprises afluorinated-polyalkylene glycol (“F-PAG”).
 12. The compound according toclaim 1, wherein n is an integer from 2 to 25; and/or wherein m is 0;and/or wherein p is 1 to
 6. 13. The compound according to claim 1 havinga viscosity at 40° C. of from about 5 to about 250 cP.
 14. A compositioncomprising at least two different compounds of formula (Ia) and/or (Ib)as defined in claim
 1. 15. A composition comprising one or morecompounds of formula (Ia) and/or (Ib) as defined in claim 1 and a heattransfer portion.
 16. The composition according to claim 14, wherein theweight percentage of the compound or compounds of formula (Ia) and/or(Ib) in the composition is 1 to 30%.
 17. The composition according toclaim 15, wherein the heat transfer portion comprises one or morecompounds selected from the group consisting of (hydro)fluoroolefins(HFOs), hydrofluorocarbons (HFCs), chlorofluorocarbons (CFCs),hydrochlorofluorocarbons (HCFCs), perfluoroalkyl iodides, andhydrocarbons.
 18. The composition according to claim 15, wherein theheat transfer portion comprises R-32, R-152a, CF₃I, R-1234ze, R-1234f,R-1132a, R-1123, R-744, R-290, and/or R-600a.
 19. The compositionaccording to claim 14, further comprising a stabiliser.
 20. Thecomposition according to claim 15, which comprises a single liquid phaseacross the entire temperature range between −30° C. and 70° C.
 21. Amethod for making the compound of formula (Ia) and/or formula (Ib),according to claim 1, comprising polymerizing an epoxide with aninitiator formed from a base and an alcohol.
 22. The method according toclaim 21, wherein the base is a group I or group II metal hydroxide. 23.The method according to claim 22, wherein the alcohol is a primaryalcohol.
 24. The method according to claim 21, comprising polymerizingthe epoxide in an absence of a solvent.
 25. The method according toclaim 21, wherein the polymerizing is carried out at a temperature offrom about 0° C. to about 130° C.
 26. The method according to claim 21,wherein the polymerizing is carried out at a pressure of from about 00to about 1000.3 kPa.
 27. The method according to claim 21 wherein thepolymerizing is of an epoxide selected from the group consisting of anepoxide of 3,3,3-trifluoropropene (1243zf), an epoxide of2,3,3,3-tetrafluoropropene (1234yf), an epoxide of1,3,3,3-tetrafluoropropene (1234ze), an epoxide of1,1,1,4,4,4-hexafluoro-2-butene (1336mzz), and3,3,3-trifluoro-2-(trifluoromethyl)-1,2-propenoxide (HFIBO).
 28. A heattransfer device comprising the composition according to claim 14.